Flame-retardant agents for thermoplastic products

ABSTRACT

COMPOUNDS HAVIN THE FORMULA   R4-P(+)(-R5)(-R6)-R7 Y(-)   WHEREIN R4 IS CARBOXYLALKENYL OR CARBOALKOXYALKENYL, R5, R6 AND R7 ARE, INDIVIDUALLY, ALKYL, ALKENYL, HYDROXY, IMIDAZOL OR CARBOXY SUBSTITUTED ALKYL, ARYYL, ARALKYL, VINYL, HALO, POLYHALO OR NITRO AR-SUBSTITUTED ARALKYL, DIALKYLAMINOALKYL OR CARBOALKOXYALKY RADICALS AND Y IS BROMINE OR CHLORINE.

United States Patent M 3,736,349 FLAME-RETARDANT AGENTS FOR THERMOPLASTIC PRODUCTS Helen Currier Gillham, Princeton, and Allan Ellis Sherr, Warren, N.J.,and Harvey Gerald Klein, New York, N.Y., assignors to American Cyanamid Company,

Stamford, Conn.

No Drawing. Division of application Ser. No. 753,739, Aug. 19, 1968, now Patent No. 3,654,342, which is a division of application Ser. No. 479,599, Aug. 13, 1965, which in turn is a continuation-in-part of application Ser. No. 296,364, July 19, 1963, now abandoned. This application Oct. 27, 1970, Ser. No. 84,484

Int. Cl. C07c 57/02, 69/52 US. Cl. 260486 R 2 Claims ABSTRACT OF THE DISCLOSURE Compounds having the formula wherein R is carboxyalkenyl or carboalkoxyalkenyl, R R and R are, individually, alkyl; alkenyl; hydroxy, imidazol or carboxy substituted alkyl; aryl; aralkyl; vinyl, halo, polyhalo or nitro ar-substituted aralkyl; dialkylaminoalkyl or carboalkoxyalkyl radicals and Y is bromine or chlorine.

CROSS-REFERENCES TO RELATED APPLICATIONS This application is a divisional of our copending application, Ser. No. 753,739, filed Aug. 19, 1968, now Pat. No. 3,654,342 which, in turn, is a divisional of our copending application, Ser. No. 479,599, filed Aug. 13, 1965, which, in turn, is a continuation-in-part of our application, Ser. No. 296,364, filed July 19, 1963, and now abandoned.

BACKGROUND OF THE INVENTION The use of various materials incorporated into thermoplastic resins in order to improve the fiame-retardance thereof has been known in the prior art. Many compounds are commercially available for such a use, among them being chlorostyrene copolymers, chlorinated paraffin wax with triphenyl stibine, chlorinated parafiins and aliphatic antimonyl compounds, as well as antimony oxide-chlorinated hydrocarbon mixtures. A drawback, however, of these compounds has been the fact that generally a large amount, i.e. upwards of 35%, of additive must be incorporated into the resin in order to make it sufliciently flame-retardant. Also these prior art additives tend to crystallize or oil out of the resin after a relatively short time of incorporation.

SUMMARY We have now found a group of compounds which may be added to thermoplastic resins in relatively small amounts and still result in the production of satisfactory flame-retardant compositions while not crystallizing or oiling out of the resin after incorporation therein.

The production of thermoplastic resin compositions which are flame-retardant, i.e. have high resistance to heat, is of considerable commercial importance. For example, such articles as castings, moldings, foamed or laminated structures and the like are required, or at least desired, to be resistant to fire and flame and to possess the ability to endure heat without deterioration. Typical illustrations of such applications can be found in castings for live electrical contacts which should not be ignited or deteriorated by heat and sparks.

DESCRIPTION OF THE INVENTION 'INCLUD- ING PREFERRED EMBODIMENTS This invention relates to flame-retardant compositions comprising thermoplastic polymers containing a flameretarding amount of a monophosphonium halide having the formula wherein R is a carboxyalkenyl radical (C -C or a carboalkoxyalkenyl radical (C -C and R R and R are, individually, alkyl (C -C alkenyl (C -C hydroxy, imidazoyl and carboxy substituted alkyl (C 8) y 6 10), aralkyl r- 11), y halo, p yhalo and nitro ar-substituted aralkyl (C y-C11), dialkylaminoalkyl (C -C or carboalkoxyalkyl (C -C radicals and Y is chlorine or bromine.

The thermoplastic polymers The thermoplastic polymers into which the flame-retardant agents may be incorporated to produce the novel compositions of the present invention are generally the vinyl type polymers wherein the monomeric material is polymerized, by any known method, via the vinyl unsaturation therein. Additionally, however, thermoset type materials may be employed such as the polyester resins, polyurethanes, and the like. Examples of the vinyl type polymers which may be used to form our novel compositions are the vinyl halides, the vinylidene halides, the vinyl acetates, polyvinylbutyral, butadiene copolymers, acrylonitrile-butadiene-styrene polymers, the acrylonitriles, etc. Additionally and preferably, one may incorporate the flame-retardant agents mentioned above into such polymers as the styrene polymers, i.e. polystyrene, etc., the a-olefin polymers, such as the homopolymers and copolymers etc. containing, as the major constitutent, ethylene, propylene, and the like and the acrylate and methacrylate polymers produced from monomers having the formula wherein R is hydrogen or a methyl radical and R is hydrogen or an alkyl radical having from 1 to 6 carbon atoms, inclusive. Examples of monomers represented by Formula III include methyl acrylate, ethyl acrylate, npropyl acrylate, isopropyl acrylate, n-butyl acrylate, tbutyl acrylate, isobutyl acrylate, n-amyl acrylate, t-amyl acrylate, hexyl acrylate and their corresponding alkyl methacrylates.

Also such polymers as the nylons, e.g. adipic acidhexamethylenediamine reaction products, the polyformaldehydes, cellulose acetate (and/or butyrate, etc.), the polycarbonates, i.e. phosgene-bisphenol A reaction products, the -so-called impact polymers, i.e. rubber-polymer 3' blends suelras blends of polystyrene with 5-10% of butadiene-styrene, etc. may be made flame-retardant by the incorporation therein of the phosphonium halides more specifically discussed hereinbelow and represented by Formulae I and II.

"Additional examples of monomers which may be used to form the thermoplastic vinyl polymers encompassed by the present invention, polymerized either singularly or in combination with each other or with the other compounds set forth hereinabove, aresuch monomers as the unsaturated alcohol esters, more particularly the allyl,

I the present i nvention, any monophosphonium halide,

methallyl, vinyl, methvinyl, butenyl, etc., unsaturated ethyl, jpropyl, isopropyl, butyl, sec.-'bu'tyl, amyl, etc.,

esters of ethylenicallyunsaturated aliphatic monobasic acids,iillustrat-ive examples of which appear above; vinyl cyclic compounds (including monovi'nyl aromatic hydrocarbons), e.g., 0-; m-- and p-chlorostyrenes, bromostyrenes, -flu0rostyrenes, -methylstyrenes, -ethy1stryenes, -cyanostyrenes, the variouspoly-substituted styrenes such, for example, as the. various di-, tri-, and tetrachlorostyrenes, -bromostyrenes, fluorostyrenes, methylstyrenes, -ethylstyrenes, -cyanostyrenes, etc., pyridine, divinyl benzene, diallyl benzene, the various allyl cyanostyrenes, the various alpha-substituted styrenes vand alpha-substituted ring-substituted syrenes, e.g., alphamethyl styrene, alpha-methyl-para-methyl styrene; etc; unsaturated ethers, e.g., ethyl vinyl ether, diallyl ether, etc.; unsaturated amides, for instance, 'N-allyl caprolactam, acrylamide, and N-substit-uted acrylamides, e.g., N-rnethylol acrylamide, N-allyl acrylamide," N-methyl acrylamide, N-phenyl acrylamide, etc.; unsaturated ketones, e.g., methyl vinyl ketone, methyl allyl ketone, etc.; methylene malonic esters, e.g., methylene methyl malonate, etc. and ethylene.

Other examples of monomers that canbe used as polymers to form the resin portion of OHfilOVfil flamevinyl retardant compositions are the vinyl halides, more pa'rticularly, vinyl fluoride, vinyl chloride, vinyl bromide and vinyl iodide, .and the various vinylidene compounds, including the vinylidene halides, e.g., vinylidene chloride, vinylidene, bromide, vinylidene fluoride, arid vinylidene iodide, other comonomers being added, if needed, in

bonate, etc. Other examples of allyl compounds that may :33; regard to Formula IL under the following conditicns:

be employed are given, for example, in US. Pat. No'. 2,510,503,issued June 6, 1950.

:These above mentioned monomers may be polymerized, copolymerized, etc., in any known mannersuch'as by free-radical generating catalysts, irradiation a'nion and cation type catalysts and'the' like, 'said'method'of'polym erization forming no part ofthe presentinv'ention. Y

The monophosphonium halides As mentioned above, We have discovered the addition of monophosphonium halides' to athermoplastic resin results in the production of resinous compositions having excellent flame-retardant properties. According to stable to processing conditions, may be used for this purpose. A preferred group of phosphonium halides, however, are those represented by Formula I. The monophosphonium halides may be incorporated into the resins in flame-retarding amounts, i.e. generally amounts ranging from about 1%, by weight, to about 35%, by weight, preferably 5% to 25%, by Weight, based on the weight of the polymer, have been found sufficient. A further group of preferred monophosphonium halide compounds useful in producing our novel compositions are those wherein three of R, R R and R are cyanoethyl or phenyl radicals. 1 These monophosphonium halides can be incorporated into the resin lay-any known method. That is to say, the flame-retardant monophosphonium halide additive may be added to the resin by milling the resin and the halide on, for example, a two-roll mill, in a Banbury mixer etc., or the halide may be added by molding the halide and resin simultaneously, extruding the halide and resin or by merely blending the resin in powder form with the halide and thereafter forming the final desired article. Additionally, the monophosphonium halide may also be added during the resin manufacture, i.e., during the monomer polymerization procedure, provided the catalyst, etc. conditions and ingredients of the polymerization system are inert to the monophosphonium halide.

The monophosphonium halides set forth hereinabove may be produced in any known manner without varying from the scope of the present invention. Various methods for the production of phosphonium halides of this type are disclosed in, for example, articles by Rauhut et al., J. Org. Chem., volume 28, page 473, 1963; Grayson et al., J. Am. Chem. Soc., volume 81, page 4806, 1959; Grayson et al., J. Am. Chem. Soc., volume 82, page 3922, 1960; US. Pat. 3,005,013 to Grayson et al., patented Oct. 17,- 1961; Rauhut et al., patent application, Ser. No. 211,412, filed July 20, 1962 and these articles and patents are hereby incorporated herein by reference. 3-Those phosphonium halides represented by Formula I may be produced by reacting a compound of the formula R Ref R2 with'a compound'haying the formula wherein-R, R 'R ,R and X are as defined above in regard to Fo'rmulal, and those represented by Formula 11 maybe produced, among other methods, by reacting a compound having the formula with a compound having the formula 1: vRat wherein R R R R and Y are as indicated above in heat, to a temperature ranging from about 0 C. to about 150 (3., a solution of the halide and tertiary phosphine in an appropriate solvent, such as butanol, acetonitrile and the like, for from 1 to 24 hours. The phosphonium halide is isolated by filtration, in the case of an insolu- The imidazolyl compounds may alternatively be prepared by reacting, under the conditions specified above, in regard to the other monophosphonium halides, a com pound such as tributylvinylphosphoniumbromide or tricyclohexylvinylphosphonium bromide, etc., with an appropriately substituted imidazole, -e.g., 2-methyl imidazole by refluxing in a suitable solvent, The products are then recovered by filtration.

The carboxyalkyl compounds may also be produced via another mechanism according to the equation:

H20 11 1 (CH2CH2COOH)2 -1 HCl [CuHafKCHzCHzCOOHsHCP CHzCHzOO O- The first step is accomplished at 80 to 105 C. under a nitrogen atmosphere for about 3 hours while the second step is conducted at room temperature and recovery is by subsequent water evaporatiom Examples of compounds which are represented by Formulae I or II and are therefore useful in producing the novel compositions of the present invention, include tetramethylphosphonium chloride, bromide and iodide, tetraethylphosphonium chloride, bromideand iodide, tetran-propylphosphonium chloride, bromide and iodide, tetraisopropylphosphonium chloride, bromide and iodide, tetra-n-butylphosphonium chloride, bromide and iodide, tet-' ra-t-butylphosphonium chloride, bromide and iodide, tetraisobutylphosphonium chloride, bromide and iodide, tetrapentylphosphonium chloride, bromide and iodide, tetrahexylphosphonium chloride, bromide and iodide, tetraheptylphosphonium chloride, bromide and iodide, tetraoctylphosphonium chloride, bromide and iodide, tetravinylphosphonium chloride, bromide and iodide, tetraallylphosphonium chloride, bromide and iodide, tetrapropenyl-l-phosphonium chloride, bromide and iodide, tetral-butenylphosphonium chloride, bromide and iodide, tetra-Z-butenylphosphonium chloride, bromide and iodide, tetra-1-or-2-pentenylphosphonium chloride, bromide and iodide, tetra-l- -2-or-3-hexenylphosphonium chloride, bromide and iodide, tetra-1-;-2-or-3-heptenylphosphonium chloride, bromide and iodide, tetra-l-;-2-;'-3-or-4- octenylphosphonium chloride, bromide and iodide, tetracyanomethylphosphonium chloride, bromide and iodide,-

tetra-2-cyanoethylphosphonium chloride, bromide and iodide, tetra-2-cyanopropylphosphonium chloride, bro mide and iodide, tetra-3-cyanopentylphosphonium chloride, bromide and iodide, tetra-Z-cyanohexylphosphonium chloride, bromide and iodide, tetra-4-cyanohexylphosphonium chloride, bromide and iodide, tetra-3-cyanoheptyl-phosphonium chloride, bromide and iodide, tetra- 6-cyanooctylphosphonium chloride, bromide and iodide, tetrahydroxymethylphosphonium chloride, bromide and iodide, tetra-Z-hydroxyethylphosphonium chloride, bromide and iodide, tetra-Z-hydroxypr'opylphosphonium chloride, bromide and iodide, tetra-3-hydroxypentylphosphonium chloride, bromide and iodide, tetra-4-hydroxyhexylphosphonium chloride, bromide and iodide, tetra-6- hydroxyheXylphosphonium chloride, bromide and iodide, tetra-3-hydroxyheptylphosphonium chloride, bromide and iodide, tetra-8-hydroxyoxtylphosphonium chloride, bromide and iodide, tetracarboxymethylphosphonium chloride, bromide and iodide, tetra-2-carboxyethylphospho nium chloride, bromide and iodide, tetra-Z-carboxypropylphosphonium chloride, bromide and iodide, tetra-3- carboxypentylphosphonium chloride, bromide and iodide, tetra-5-carboxyhexylphosphonium chloride, bromide and iodide, tetra-7-carboxyheptylphosphonium chloride, bromide and iodide, tetra-l-carboxyoctylphosphonium chloride, bromide and iodide, tetraimidazolylmethylphosphonium chloride, bromide and iodide, tetra-Z-imidazolylethylphosphonium chloride, bromide and iodide, tetra-3- imidazolylpropylphosphonium chloride, bromide and iodide, tetra-5-imidazolylpentylphosphonium chloride, bromide and iodide, tetra-Z-imidazolylbutylphosphonium chloride, bromide and iodide, tetra-3-cyanobutylphosphonium chloride, bromide and iodide, tetra-B-hydroxybutylphosphonium chloride, bromide and iodide, tetra-4-carboxybutylphosphonium chloride, bromide and iodide, tetra-2-imidazolylhexylphosphonium chloride, bromide and iodide, tetra 3 imidazolylheptylphosphonium chloride, bromide and iodide, tetra-8-imidazolyloctylphosphonium chloride, bromide and iodide, tetraphenylphosphonium chloride, bromide and iodide, tetratolylphosphonium chloride, bromide and iodide, tetraxylylphosphonium chloride, bromide and iodide, tetra-u-methylphenylphosphonium chloride, bromide and iodide, tetranaphthylphosphonium chloride, bromide and iodide, tetrabenzylphosphonium chloride, bromide and iodide, tetra-Z-phenethylphosphonium chloride, bromide and iodide, tetraa-methylbenzylphosphonium chloride, bromide and iodide, tetra-u-ethylbenzylphosphonium chloride, bromide and iodide, tetra 4 phenylbutylphosphonium chloride, bromide and iodide, tetra-5-phenylpentylphosphonium chloride, bromide and iodide, tetra(o, m or p-vinylbenzyl)phosphonium chloride, bromide and iodide, tetra- (o, m or p-chloro, bromo, fluoro or iodobenzyDphosphonium chloride, bromide and iodide, tetra(o, m or p dichloro, dibromo, difluoro or diiodobenzyl)phosphonium chloride, bromide, and iodide, tetra(o, m or p-nitrobenzyDphosphonium chloride, bromide and iodide, tetra(o, m or p-vinyl-Z-phenethyl)phosphonium chloride, bromide and iodide, tetra(o, m or p-chloro-Lphenethyl), phosphonium chloride, bromide and iodide, tetra(o, m or p-dibromo-Z-phenethyl)phosphonium chloride, bromide and iodide, tetra(o, m or p-nitro-Z-phenethyl)phosphonium chloride, bromide and iodide, tetra- (o, m or p-vinyl-a-methylbenzyl)phosphonium chloride, bromide and iodide, tetra(o, m or p-fluorow-methylbenzyl)phosphonium chloride, bromide and iodide, tetra- (o, m or p-trichloro-a-methylbenzyl)phosphonium chloride, bromide and iodide, tetra(o, m or p-nitro-a-methylbenzyDphosphonium chloride, bromide and iodide, tetranaphthylrnethylphosphonium chloride, bromide and io dide, tetra(vinyl, chloro, dibromo or nitro ar-substituted naphthylmethyl)phosphonium chloride, bromide and iodide, tetra(dimethylaminomethyl)phosphonium chloride, bromide and iodide, tetra(diethylaminomethyl)phosphonium chloride, bromide and iodide, tetra(diethylaminoethyl)phosphonium chloride, bromide and iodide, tetra- (butylmethylaminomethyl)phosphonium chloride, bromide and iodide, tetrakis (carbomet hoxymethyl)phosphonium chloride, bromide and iodide, tetra'kis(carboethoxymethyDphosphonium chloride, bromide and iodide, tetrakis(carbomethoxyethyl)phosphonium chloride, bromide and iodide, tetrakis(Z-carboethoxyethyl)phosphonium chloride, bromide and iodide, tetrakis(3-carboethoxy-propyDphosphonium chloride, bromide and iodide, tetrakis(2 carbopropoxyethyl)phosphonium chlo ride, bromide and iodide, tetrakis(carbobutoxymethyl) phosphonium chloride, bromide and iodide, tetrakis(3- carbopropoxypropyl)phosphonium chloride, bromide and 'iodide, tetrakis(carbopentoxymethyl)phosphonium chloride, bromide and iodide, tetrakis(4-carboethoxybutyl) phosphonium chloride, bromide and iodide, tetrakis(carbomethoxyvinyDphosphonium chloride, bromide and iodide, tetrakis(Z-carbomethoxyallyl)phosphonium chloride, bromide and iodide, tetrakis(carboethoxyvinyl)phosphonium chloride, bromide and iodide, tetrakis(carbobutoxyvinyl)phosphonium chloride, bromide and iodide, tetrakis(2 carbomethoxy-Z-butenyl)phosphonium chloride, bromide and iodide, tetrakis(2-carbomethoxy-3-pentenyl)phosphonium chloride, bromide and iodide, methyltriphenylphosphonium chloride, bromide and iodide, ethyltriphenylphosphonium chloride, bromide and iodide, propyltriphenylphosphonium chloride, bromide and io- 7 dide, benzyltriphenylphosphonium chloride, bromide and iodide, p-nitrobenzyltriphenylphosphonium chloride, bromide and iodide, 2,4-dichlorobenzyltriphenylphosphonium chloride, bromide and iodide, carboethoxymethyltriphenylphosphonium chloride, bromide and iodide, tris(2-cy anoethyl)methylphosphonium chloride, bromide and iodide, tris(2-cyanoethyl)-ethylphosphonium chloride, bromide and iodide, tris(2-cyanoet-hyl)octylphosphonium chloride, bromide and iodide, tris(2-cyanoethyl)allylphosphosphonium chloride, bromide and iodide, benzyltris(2- cyanoethyDphosphoninm chloride, bromide, and iodide, 2,4-dichlorobenzyltris(2 cyanoethyDphosphonium chloride, bromide and iodide, 2,5-dichlorobenzyltris(Z-cyanoethyl)phosphonium chloride, bromide and iodide, 3,4-dichlorobenzyltris(2 cyanoethyDp-hosphonium chloride, bromide and iodide, 2,4-diiodobenzyltriphenylphosphonium chloride, bromide and iodide, 2,5-difluorobenzyltriphenylphosphonium chloride, bromide and iodide, 3,4- dibromobenzyltriphenylphosphonium chloride, bromide and iodide, 2-hydroxyethyltriphenylphosphonium chloride, bromide and iodide, tris(2-cyanoethyl)-2 hydroxyethylphosphonium chloride, bromide and iodide, trib-utylbenzylphosphonium chloride, bromide and iodide, tributylvinylphosphonium chloride, bromide and iodide, bis- (2 hydroxypropyl)diphenylphosphonium chloride, bromide and iodide, 2-hydroxypropylmethyldiphenylphosphonium chloride, bromide and iodide, tributyl-2,4-dichlorobenzylphosphonium chloride, bromide and iodide, 2,5-dichlorobenzylphosphonium chloride, bromide and iodide, 3,4-dichlorobenzylphosphonium chloride, bromide and iodide, tris(2-cyanoethyl)-o-vinylbenzylphosphonium chloride, bromide and iodide, tris(2-cyanoethyl)-p-vinylbenzylphosphonium chloride, brdmide and iodide, tris(2- cyanoethyl) m vinylbenzylphosphonium chloride, bromide and iodide, triphenyl-o, m and p-vinylbenzylphosphonium chloride, bromide and iodide, tris(2-carboxyethyDphosphonium chloride, bromide and iodide, bis(2- carboxyethyl)bis(2 cyanoethyDphosphonium chloride, bromide and iodide, tributyl-(o, m and p-vinylbenzyl) phosphonium chloride, bromide and iodide, ethyltriphenylphosphonium chloride, bromide and iodide, 2-l1ydroxyethyltriphenylphosp honium chloride, bromide and iodide, tributyl[2-(2-rnethyl 1 imidazolyl)ethyl1phosphonium chloride, bromide and iodide, tricyclohexyl[2-(2-methyl-l-imidazolyl)ethyl]phosphonium chloride, bromide and iodide, tributyl(diethylaminoethyl)phosphonium chloride, bromide and iodide, 2 butenylbis(2 cyanoethylphenylphosphonium chloride, bro-mide and iodide, 4-octenyl(2- hydroxyethyl)methylphenylphosphonium chloride, bromide and iodide, 2-cyanoethyl(4-cyanobutyl)diphenylphosphonium chloride, bromide and iodide, diet-hylphenyl(4-hydroxybutyl)phosphonium chloride, bromide and iodide, allylbenzyl(8 hydroxyoctylmethylphosphonium chloride, bromide and iodide, carboethoxyethyl(8-cyanooctyl)diphenylphosphonium chloride, bromide and iodide, bis(8-carboxyoctyl) dimethylphosphonium chloride, bromide and iodide, bis(2-cyanoethyl) (p-bromobenzyDphenylphosphonium chloride, bromide and iodide, bis(2-cyanoethyl) (4-carboxybutyl)phenylphosphonium chloride, bromide and iodide, bis (Z-cyanoethyl)naphthylphenylphosphonium chloride, bromide and iodide, diphenylmethyl [4-(2-methyl l imidazolyl)butyl]phosphoniu-m chloride bromide and iodide, tris(2-cyanoethyl) (2-methylnaphthyDphosphonium chloride, bromide and iodide, tris(2-cyanoethyl) 2,4 (dibromobenzyl)phosphonium chloride, bromide and iodide, methyldiphenyl[8-(2-methyl-l-imidazolyl)ootyl] phosphoniu-m chloride, bromide and iodide, diphenylmethyl(p-iodobenzyl)phosphonium chloride, bromide and iodide, tris(2-cyanoethyl)(3-chloro-2- methyl-naphthyDphosphonium chloride, bromide and idide, tributyldimethylaminoethylphosphonium chloride,

bromide and iodide, 2-carboethoxypropyltriphenylphosphonium chloride, bromide and iodide, carbooctoxymethyltriphenylphosphonium chloride, bromide and iodide, dibutylaminoethyltrimethylphosphonium chloride, bromide and iodide, dibenzyl(p-chlorobenzyl)propylphosphonium chloride, bromide and iodide, cyanomethyltrimethylphosphonium chloride, bromide and iodide, butyltris(p nitrobenzyl)phosphonium chloride, bromide and iodide, tetra-B-carboxypropenyl-l-phosphonium chloride, bromide and iodide, tetra-Z-carboxyvinyl propenyl-l-phosphonium chloride, bromide and iodide, trimethyl-3-carboxypropenyll-phosphonium chloride bromide and iodide, triphenyl-2-carboxyvinyl-l-phosphonium chloride, bromide and iodide, and the like, mixtures thereof, other phosphonium halides having mixed substituents and the like.

Examples of compounds represented by Formula II, above, i.e. the novel compounds of the instant invention, include tris(2 cyanoethyl) 2-carbomethoxyvinylphosphonium chloride and bromide, tris(2-cyanoethyl)-2-carbomethoxypropenyl-3-phosphonium chloride and bromide, triphenyl 4-carbomethoxybutenyl-4-phosphonium chloride and bromide, triphenyl-Z-carbomethoxypropenyl- 3-phosphonium chloride and bromide, tributyl-Z-carbomethoxypropenyl-3-phosphonium chloride and bromide, tributyl 5 carbomethoxypentenyl-2-phosphonium chloride and bromide, tributyl-Z-carbomethoxyhexenyll-phosphonium chloride and bromide, tris-(Z-cyanoethyl)-2-carboethoxyvinyl phosphonium chloride and bromide, tris(2 cyanoethyl) 3-carbobutoxypropenyl-3- phosphonium chloride and bromide, dioctylvinyl-Z-carbomethoxypropenyl-3-phosphonium chloride and bromide, tris(2 hydroxyethyl) 2-carbomethoxypropenyl- 3-phosphonium chloride and bromide, bis(l-carboxypropyl)methyl 2 carbomethoxypropenyl 3 phosphonium chloride and bromide, methylnaphthylphenyl- 2 carbomethoxypropenyl 3 phosphonium chloride and bromide, dibenzylethyl 2 carbomethoxypropenyl- 3-phosphonium chloride and bromide, p-nitrobenzyltris- (2-carbomethoxypropenyl-3) phosphonium chloride and bromide, tris (dimethylaminoethyl) Z-carbomethoxypropenyl-3-phosphonium chloride and bromide, tris(2-carbomethoxyethyl) 2 carbomethoxypropenyl 3-phosphonium chloride and bromide, tris(2-cyanoethyl)-3-carboxypropenyl-l-phosphonium chloride and bromide, tributyl-Z-carboxyvinyl phosphoniurn chloride and bromide, tetra(2-cyanoethyl)phosphonium bromide, mixtures thereof, other compounds having mixed substituents and the like.

It is also within the scope of the present invention to incorporate such ingredients as plasticizers, dyes, pigments, stabilizers, antioxidants, antistatic agents and the like to our novel compositions.

The following examples are set forth for purposes of illustration only and are not to be construed as limitations on the present invention except as set forth in the appended claims. All parts and percentages are by weight unless otherwise specified.

Any appropriate fiame-retardance test may be used to determine the flame retardance properties of any specific compound. One test which is reasonably efiicient is that designated as a modified version of ASTM test D-635-56T. The specifications for this test are: a specimen, 5" in length, 0.5" in width and 0.045" in thickness, is marked at the 1" and 4" lengths and is then supported with its longitudinal axis horizontal and its transverse axis inclined at 45 to the horizontal. A Bunsen burner with a 1" blue flame is placed under the free end of the strip and is adjusted so that the flame tip is just in contact with the strip. At the end of 30 seconds, the flame is removed and the specimen is allowed to burn. If the specimen does not continue to burn after the first ignition it is immediately recontacted with the burner for another 30 second period. If, after the two burnings, the strip is not burned to the 4" mark, the specimen is designated as selfextinguishing or flame-retardant.

EXAMPLE 1 parts of polyethylene and 15 parts of triphenylmethylphosphonium bromide are milled together on a two roll mill at about 170 C. The resulting milled composition is molded into strips 5" in length, 0.5 wide and 0.45! in thickness and said strips are then subjected to the above specified flame-retardance test. The strips pass the test and are therefore designated as flame-retardant.

Following the procedure of Example 1, the following examples were carried out utilizing different flameretardant agents and various thermoplastic resin polymers. The results of these examples are set forth in Table I below. In each instance, the resultant plastic-mouophosphonium halide mixture passed the flame-retardance test and was designated as flame and fire-retardant. In the table, PE=polyethylene; PP=polypropylene; PMMA: poly(methylmethacrylate); PA=poly(acrylic acid); PS: poly(styrene); PF polyformaldehyde; CA=cellulose acetate; PC=polycarbonate (Bisphenol Aphosgene reaction product); AN=acrylnitrile; ST=styrene and BD butadiene. The term nylon refers to the reaction product of adipic acid and hexamethylene diamine.

TABLE I Flame retardant Poly- Per- Example mer R R R R X cent 2 Q Q CH3 Same as above Same as above Same as above CH I do do do CHaCHz Br do C a( 2)2 Br 7 do CH =CHCH1 Br 30 do do dn ()1 20 dn (In Same 3.5 above B! do do do I 15 do do I 15 do do Br 20 OzN -CH,

12 PP an dn C1 15 Cl CH:

13 PE do do do Sameasabove O1 15 14 PE do do (I? Br 20 CHQOHZO C CH NCCHQCHZ NGCHzCH: NCCHzCHz CH3 I 10 NCCHzCHa NCCHzCHz NCCH2CH2 CH3 I 10 NCCHzCHz NCCHzCHfl NCCHzCHz CH3CH2 B1 20 NCCH2CH3 NOCHZCHQ NCCHZCHZ CH (CH2)1 Br NCCHzCHg NOCHQCHQ NCCHzCHz CHZZCHCHZ B1 NCCHzCHg NCCHflCHZ NCCHzCHg CH2=CHCH3 Br 20 NCCHaCHz NCCHzCHz NCCHzCHz CHz=CHCHz Cl 30 NCOHZCHi NOOHzOHa NCCHzCHz Q CH 01 25 NCCHzCHg NCCHzCHa NCCHzCHr Same as above B1 30 NCOHzCHa NCCHzCHz NCCHaCHz I 15 25 PP NCCHzCHg NCCH2CH2 NCCHzCHz Same as above I 15 PE NCCH2CH2 NC OH2C 2 NCCHzCHz Mixed isomers of- 2 i CH3 27 PE HOCHZCHQ B1- 15 CHaCHaCHzCH: CHaCHzCHz CH CH CfizCHsCHg CHgCHzCHgCHg Same as above- NOCHzCHs CHsCHzCHgCHz CHzCHzCHzOHz CHaCHzCHzCHz CHaCHzCHgCHg CHafilHCHg NCCHzCHI CHaCHzCHzCHg CHaCHzCHzCH; CH CH2CH2CH2 OH3CHZCH2OH1 Same as above NCCHnCHg Same as above I HOCHzCHz Br TABIMntlnuad Example Tertiary phosphine Halide Temp., Time, Yield, Product 0. hours Solvent percent 109 15 parts of bis(p-nitro- 9 parts of ethyl 2- 80 1. do 87 2-carboethoxypropenyl-K-methyl phenetliyl) methyl (bromoethyl) acrylate. v bis(p-nitrophenethyl) phosphine. phosphonium bromide.

110 26 parts of tris(dimethylparts of ethyl 2- 75 3 -do 75 2-carboethoxy3-tris(dimethylaminoethyl) phosphine. (bromoethyl acrylate. itminogthyl) phosphonium romi e.

111 9 parts of tris(carbo- 6 parts of methyl 4- 73 3 Butanol.. 82 4-carbomethoxy-1-buten-1-ylmethoxymethyl) bromo-4-pentenoate. tris(carbomethoxymethyl) phosphine. phosphonium bromide.

112 5 parts of trivinyl 3 parts of 2chloroacrylic 78 2. 5 Acetoni- 91 l-carboxyvlnyltrlvinyl phosphonium phosphine. acid. trile. c oride.

113 42 parts of biS(2-carparts of 4-c h1oro-3- 65 4 do 88 Bis(2carboxyethyl) 3-carboxyproboxyethyl) phenyl bntenoic acid. penyl-l phenyl phosphonium chlophosphine. ride.

11L 17 parts of dimethyl (p- 8 parts of propyl-3- 4 d0 93 2-carbopropoxyvinyl-dimethyl-pvinylbenzyl) bromoacrylate. vinylbenzyl phosphonium brophosphine. mide.

115 19 par Of His (P- 10 Darts 0f yl-2-(2- 4 do 71 2carboethoxy-l-butent-yl-tris (pbromobenzyl) chloroethyl) acrylate. bromobenzyl) phosphonium chlophosphine. ride.

116 10 parts of tris(2- 10 parts of ethyl 5-bromo 60 4 .do 52 d-carboethoxy-l-buten-l-yl-trls (2- dimethylaminobutyl) -pentenoate. dimethylaminobutyl) phosphw phosphine. nium bromide.

117 14 parts of tris(1-carbo- 8 parts of 3-chloroacrylic 75 3 do Tris(1-carboethoxypropyD-2-carettlioxygiropyl) acid. boxyvinyl phosphonium chloride. p osp me;

118 25 parts of tris(2- 30 parts of 2- bromo- 80 4 -do Tetra(2-cyanoethyl) phosphonium cyanoethyl) phosphme. propionltnle. bromide.

l 0.1 part hydroquinone added to retard polymerization.

What is claimed is: 2. A compound according to claim 1 wherein R R 1. A compound having the formula and R" are butyl, R is 2-carbomethoxypropenyl-3 and Y is chlorine. R R

f 'Y- 30 No references cited. 30 1 wherein R is selected from the group consisting of carboxy-alkenyl (C -C and carboalkoxyalkenyl radicals, R 35 R and R are, individually, alkyl (C -C radicals and Y is selected from the group consisting of chlorine and bromine.

LORRAINE WEINBERGER, Primary Examiner R. S. WEISSBERG, Assistant Examiner US. Cl. X.R.

260309, 465 D, 465 H, 465.4, 469, 471 R, 482 R, 484 R, 485 H, 486 R, 515 R, 526 R, 526 N, 534 R, 535 'R, 537 N 

